Details

Autor(en) / Beteiligte

• Hausmann, David
• Eich, Andreas
• Feldmann, Claus

Titel

The mixed valence iodine chlorides [PCl4]2[ICl2][ICl4] and [BnMe3N]2[I2Cl3][ICl4]

Ist Teil von

• Journal of molecular structure, 2018-08, Vol.1166, p.159-163

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2018

Link zum Volltext

Quelle

Elsevier ScienceDirect Journals Complete

Beschreibungen/Notizen

• The interhalides [PCl4]2[ICl2][ICl4] (1) and [BnMe3N]2[I2Cl3][ICl4] (2) were prepared by halogen exchange reaction of the interhalogen ICl3 or [BnMe3N][ICl4] (Bn: benzyl) with the strong Lewis acid PBr5 and the soft Lewis acid BiBr3 in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PCl4]2[ICl2][ICl4] (1) consists of tetrahedral [PCl4]+ cations as well as the iodine chloride anions [ICl2]– and [ICl4]–. [BnMe3N]2[I2Cl3][ICl4] (2) contains [BnMe3N]+ cations and [I2Cl3]– as well as [ICl4]– anions. Such combination of iodine chloride anions – [ICl2]–/[ICl4]– and [I2Cl3]–/[ICl4]– – is observed for the first time. Moreover, interhalides containing mixed-valent iodine as observed here with I+I and I+III are observed for the first time. In fact, a combination of I+I/I+III is yet only known for iodine oxides. Both compounds are characterized by crystal structure analysis. They are highly reactive and sensitive to temperature, light and moisture. The preparation of the iodine chlorides, moreover, points to the benefit of ionic-liquid-based synthesis for obtaining highly sensitive compounds, in general. [Display omitted] •Ionic-liquid-based synthesis of the novel interhalides.•[PCl4]2[ICl2][ICl4] consists of [PCl4]+ and [ICl2]– and [ICl4]–.•[BnMe3N]2[I2Cl3][ICl4] contains [BnMe3N]+ and [I2Cl3]– and [ICl4]–.•Combination of [ICl2]–/[ICl4]– and [I2Cl3]–/[ICl4]– and interhalides with mixed-valent iodine (I+I and I+III) observed for the first time.